JP2001520946A - Method and apparatus for treating articles containing oxidizing organic compounds - Google Patents

Abstract

An apparatus includes providing an article having an oxidizable organic compound and an organoleptic compound; advancing the article toward a means for treating the article, the means for treating the article including a treating medium, and a means for applying the treating medium to the article; and applying the treating medium to a surface of the article so as to lower the amount of the organoleptic compound in the article.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates generally to methods and apparatus for treating articles containing oxidizing organic compounds, particularly for treating films exposed to actinic radiation.

BACKGROUND OF THE INVENTION It is well known that by limiting the exposure of an oxygen sensitive product to oxygen, the quality and shelf life of the product is maintained and enhanced. For example, by limiting the oxygen exposure of oxygen-sensitive food products in a packaging system, the quality of the food product can minimize nutrient loss, slow down enzyme and lipolytic oxidation, prevent photodegradation, and reduce spoilage. Is maintained by reducing Further, such packaging retains the product in inventory longer, thereby reducing restocking and disposal costs.

[0003] One means for limiting the exposure of a product to oxygen involves the inclusion of oxygen scavengers within the packaging structure itself. This provides a more uniform removal effect over the entire package. This may be particularly important if the air circulation inside the package is restricted. Further, such inclusions block and eliminate oxygen as it penetrates the walls of the package (referred to herein as "active oxygen barriers"), thereby minimizing the overall packaging. Means may be provided to maintain possible oxygen levels.

[0004] Oxygen scavengers that can be included in the film structure are disclosed in US Pat.
Nos. 310,497, 5,350,622 and 5,399,289 (
Spear et al.), And a method for introducing oxygen scavenging is disclosed in US Pat.
No. 1,875 (Spear et al.). All of these four patents are incorporated herein by reference in their entirety. U.S. Pat. No. 5,350,622
The oxygen scavenger is manufactured from ethylenically unsaturated hydrocarbons and transition metal catalysts. Preferred ethylenically unsaturated hydrocarbons may be substituted or unsubstituted. "Oxygen scavenger" materials disclosed by Spear et al. Are compounds that consume, deplete or reduce the amount of oxygen from a given environment.

[0005] Other oxygen scavengers that can be included in the film structure are described in PCT Patent Publication No. WO 94/12590 (Commonwea).
lth Scientific and Industrial Research
ch Organization)). These oxygen scavengers include at least one reducing organic compound that is reduced under certain conditions, ie, a reduced form of a compound that can be oxidized by molecular oxygen (reduction and / or subsequent oxidation of this organic compound). Occurs independently of the presence of the transition metal catalyst). The reducing organic compound is preferably a quinone, a photoreducing dye or a carbonyl compound having an absorbance in the UV spectrum.

[0006] Oxygen scavengers are available from MAP (modified atmosphere packaging).
area packaging) and barrier packaging environments. However, oxygen scavengers often require triggering to activate oxygen scavenging properties, or at least an advantage therefrom.

No. 08 / 691,829, filed Aug. 2, 1996, which is incorporated herein by reference in its entirety, has advantages in activating oxygen scavenger films. An apparatus is disclosed. This device is particularly useful when used in a food processing plant or other facility where the actuation device is located near the packaging machine. With this arrangement, the oxygen scavenger film can be activated just prior to using the film to package food or other oxygen sensitive products, perhaps a few seconds before.

[0008] While these techniques offer great potential in packaging applications, oxygen scavenger structures can sometimes adversely affect the taste and / or odor (ie, organoleptic properties) of the packaged one. It has been found that reaction by-products can be generated. These by-products can include acids, alcohols, alkenes, dienes, esters, aldehydes and ketones.

[0009] The technical solution to this problem is described in WO 12, published on September 12, 1997.
Nos. 97/32924 and WO 97/32925, both of which are incorporated herein by reference in their entirety. These publications disclose various functional barrier materials suitable for use in multilayer oxygen scavenger films. These functional materials are characterized by the amount of extractables, such as aldehydes, and the undesired organoleptic transfer resulting from the absorption of low molecular weight by-products of the oxygen scavenging reaction.
The degree of lectic transfer is reduced.

[0010] We believe that these technical solutions provide a beneficial improvement in reducing organoleptic off-odors and off-flavors extractables in oxygen scavenging films. Although provided, further improvements have been found to be beneficial. In an oxygen scavenger system as described herein, the production of extractables is believed to be caused by two events.

[0011] The first event is actinic radiation onto the oxygen scavenger film, as occurs in a chamber of an actuation unit of the type described herein and in US patent application Ser. No. 08 / 691,829. For example, ultraviolet light is incident. This procedure is known to "activate" the film and lead to the activation (usually within a short time) of the oxygen scavenger in the film. Unfortunately, this method is also believed to result in, for example, photolytic degradation or destruction of the materials in the film at the film surface and the production of organic substances such as aldehydes and ketones as a by-product of the method.

The second event is the time at which the now activated film actually activates, ie begins to scavenge oxygen. At this stage, oxidizing organic compounds present in the film or other article begin to oxidize, producing additional organic substances (aldehydes, ketones, etc.) as by-products of the oxygen scavenging reaction.

The time elapsed between these two events is known as the induction time or induction period of the article.

In some cases, the article, such as a film, may not be exposed to actinic radiation and still adversely affect the organoleptic properties of the product to be contained within or packaged by the article Organic compounds that can provide

[0015] The inventors have discovered that the benefits of reduced extractables and enhanced, ie, improved organoleptic properties, have been attributed to simultaneous and / or exposure of articles to actinic radiation, eg, UV light. Later, preferably immediately after this event, more preferably during the induction phase,
It has been found that it can be obtained by processing the article. The present invention provides an effective method and apparatus for reducing the amount of extractables in an activated article containing an oxidizing compound as compared to methods and apparatuses that do not have the advantages of the present invention.

[0016] The method and apparatus preferably provide for treating the article before, and more preferably, immediately prior to packaging the oxygen-sensitive product with the article.

Preferably, the invention provides a spatially compact processing means.

Preferably, a device is provided which is easily integrated in-line into existing packaging systems.

In some cases, the oxygen scavenger article may not need to be exposed to actinic radiation to activate the scavenging function of the article. Nevertheless, organic products are present and / or generated by the oxygen scavenging process, and these products sometimes cause sensory irritation of the product to be contained in or packaged with the article. May adversely affect properties. The present invention will also be advantageous in reducing the amount of such organic compounds in such systems.

In still other cases, an article such as a film may contain organoleptic compounds as defined herein, even though the article does not contain an oxidizing organic compound. Here again, the present invention can be beneficially used to reduce the amount of such organoleptic compounds in articles.

Definitions As used herein, "film" means a film, laminate, sheet, web, coating, and the like, that can be used to package a product.

As used herein, “amorphous silica” refers to silica that contains no or substantially no crystalline SiO ₂ tetrahedron as measured by X-ray diffraction.

As used herein, “oxidizing organic compounds”, “oxygen scavengers” and the like are compositions that are capable of consuming, depleting or reacting with oxygen from a given environment,
Compounds, articles and the like.

As used herein, “actinic radiation” and the like means any form of electromagnetic radiation, such as ultraviolet or visible light, capable of causing a chemical change, and is disclosed in US Pat.
875 (Spear et al.).

As used herein, “polymer” and the like means a homopolymer, but also a copolymer thereof including a bispolymer, a terpolymer and the like.

As used herein, “sensory irritation” refers to the perceived flavor and / or odor of a food or non-food product contained in a package made by the method or apparatus of the present invention. Point.

As used herein, a “sensory stimulant compound” can adversely affect the organoleptic properties of a food or non-food product contained in a package made by the method or apparatus of the present invention. Refers to compounds, especially organic compounds.

As used herein, “room temperature” is an ambient temperature between 20 ° C. and 25 ° C. (68 ° F. and 77 ° F.).

SUMMARY OF THE INVENTION In a first aspect of the present invention, a method comprises providing an article containing an oxidizing organic compound and a organoleptic compound, wherein the article comprises means for treating the article. Advancing toward the article, wherein the means for treating the article includes a treatment medium and means for applying the treatment medium to the article, and applying the treatment medium to the surface of the article to provide a sensory feel in the article. Reducing the amount of the irritating compound.

[0030] In a second aspect of the invention, an apparatus reduces an amount of an organoleptic compound in an article, the article containing the oxidizing organic compound and the organoleptic compound. Means for treating the article such that the means for treating the article includes a treatment medium and means for applying the treatment medium to the surface of the article, and the article,
And means for advancing the article toward means for processing.

DETAILED DESCRIPTION OF THE INVENTION A detailed description of preferred embodiments of the present invention is as follows with reference to the accompanying drawings.

The present invention can be used in connection with various manufactured articles, compounds, material compositions, paints, and the like. Two preferred forms are sealing compounds and flexible films, both useful in packaging food and non-food products. In addition to caps and closures and traditional flexible film applications, the present invention relates to a system for oxygen scavenger activated semi-rigid packaging, rigid containers, foamed and unfoamed trays and paperboard liners. Can be used.

It is known to use sealing compounds in the manufacture of gaskets for the rigid container market. Large, wide diameter gaskets are typically manufactured using liquid plastisols. This plastisol is a very viscous liquid suspension of polymer particles in a plasticizer. In the manufacture of metal or plastic caps, lids, etc., this liquid plastisol is applied to an annular portion of a container, such as a jar, and the container with the applied plastisol is "fused" in an oven.
x) "to allow the plastisol to solidify in the gasket. This results in a gasket formed around the annular portion of the container.

Smaller gaskets are typically manufactured for use with beer crowns in bottles. A polymer melt is applied to the entire inner surface of the crown by cold forming. In this application, both poly (vinyl chloride) (PVC) and other polymers are used.

The plastic cap disc is typically manufactured by obtaining a ribbon of gasket material, making the disc, and inserting the disc into the plastic cap.

In these applications, when an article containing an oxidizing organic compound is activated by exposure to actinic radiation, treating the article during and / or after activation may result in a sensory effect in the article. The amount of irritating compound can be advantageously reduced.

The present invention relates to fresh red meats such as beef, pork, lamb and veal, sliced turkey, smoked and processed meats such as pepperoni, ham and bologna sausage, tomato based products such as It can be used in the packaging of a wide variety of oxygen sensitive products, including vegetable products, pasta and other food products, including baby food, beverages such as beer, and electronic components, pharmaceuticals, medical products and the like. The present invention
It can be easily adapted to various vertical filling and sealing (VFFS) and horizontal filling and sealing (HFFS) packaging lines.

Films suitable for use in the present invention contain an oxidizing organic compound,
Preferably, both the oxidizing organic compound and the transition metal catalyst are contained. Optionally, the oxygen scavenger film may also contain a photoinitiator composition, an antioxidant and other additives, for example, as disclosed in US Pat. No. 5,211,875. . Preferred films contain a substituted or unsubstituted ethylenically unsaturated hydrocarbon polymer oxidizable organic compound, preferably having a molecular weight of at least 1000. More preferably, the oxidizing organic compound is a styrene / butadiene copolymer, styrene / isoprene copolymer, polybutadiene,
It is selected from the group consisting of polyisoprene or a mixture thereof.

The transition metal catalyst of the oxygen scavenger is preferably a transition metal salt of cobalt, manganese or a mixture thereof. Other suitable transition metal catalysts are described in US Pat. No. 5,211,
No. 875.

[0040] The ethylenically unsaturated hydrocarbon and transition metal catalysts may further comprise one or more of the following, such as thermoplastic polymers typically used to form film layers in plastic packaging products.
One or more polymer diluents can be combined. In the manufacture of certain packaging products, it is also possible to use thermosetting resins known as polymer diluents. Polymers that can be used as diluents include, but are not limited to, polyethylene terephthalate (PET), polyethylene, low or very low density polyethylene, ultra low density polyethylene, linear low density polyethylene, polypropylene, poly Includes vinyl chloride, polystyrene and ethylene copolymers such as ethylene-vinyl acetate, alkyl ethylene- (meth) acrylate, ethylene- (meth) acrylic acid and ethylene- (meth) acrylic ionomer.
Blends of different diluents can also be used. The choice of polymer diluent will depend, in part, on the product to be manufactured and the end use.

By exposing the oxygen scavenger film to actinic radiation at a constant wavelength, intensity, residence time and distance from the film, the oxygen scavenging properties of the film are activated. UV-C light, such as germicidal wavelength UV light, has been found to be particularly effective in activating oxygen scavenger films. Preferred wavelengths are between 200 and 280 nm, for example 254 nm.

As described in US patent application Ser. No. 08 / 691,829 (incorporated herein by reference in its entirety), the oxygen scavenger film to be actuated has at least a desired wavelength. 100 mJ / cm ² , preferably at least 200 mJ
/ Cm ² , more preferably 300 to 1600 mJ / cm ² , most preferably 4
The dose of the actinic 00~800mJ / cm ² at a sufficient intensity and residence time to give to the film is exposed to actinic radiation. Within this range, preferably at least 5
Different doses of actinic radiation in combination with an environment at a temperature of 5 ° F. advantageously affect the removal rate of the film after activation.

The intensity and residence time of actinic radiation can be utilized to provide the desired dose to a particular film. The film actuating of at least 0.8 mW / cm ^2, more preferably it is preferred to exposure to actinic radiation at an intensity of 2.0 mW / cm ^2. To provide a very long without film path, the film to be activation, more preferably exposed to actinic radiation at an intensity of 3.0~10mW / cm ^2, for example 3.0~7.5mW / cm ² . This strength is preferably between 1 cm and 3 cm,
It is given by the distance from the actinic radiation source to the film.

The desired dose of actinic radiation can be provided to a particular film by traversing the film over a path having a particular length to which the film is exposed to actinic radiation. At the strength as described above, the oxygen scavenger film is preferably
. Over a film path having a length of 5 m to 12 m, preferably 2 to 4 m,
. It is usefully activated at an average moving speed of the film along the path of 5 m / min to 30 m / min, typically 1.2-4 m / min. This procedure typically results in 15-90
The exposure time of the film to UV-C light is in seconds. With the above-mentioned wavelength, intensity and residence time of UV-C light, the oxygen scavenger film has an excellent oxygen scavenging rate.
It has been found that it can be activated with a very short or negligible induction phase, whereby the method of the invention exists so that the oxygen scavenger film can be activated at the time of packaging or shortly before packaging. It allows for in-line incorporation into the packaging process, ameliorating the problems associated with storing and stocking activated oxygen scavenging films.

The oxygen scavenger film thus activated, depending on the formulation and type of packaging to which the film is applied, can be measured at 40 ° F. when measured 4 days after activation.
An oxygen removal rate of 1 cc / ^{m 2} / day ~100cc / ^{m 2} / day at temperatures of (4 ° C.). Modified Atmosphere Packaging (MAP) with Modified Atmosphere Headspace (M
AP, _{1~2% O} 2), oxygen scavenging films activation, as measured after 4 days by activation, an oxygen removal rate of 20~66cc / ^{m 2} / day at 4 ° C..

FIG. 1 shows an unwind roll 12 for feeding the film 8 to the chamber 9, a series of rollers 14 defining a film path 16 through the chamber 9, and a film activated for the next use. 1 shows a stand-alone actuation device 10 with a take-up roll 18 for receiving the same. The chamber 9 contains an actinic radiation source, for example, a bank (b).
an) a series of low pressure germicidal UV lamps 20 disposed in a film passage 16 and a film passage 16 is provided to the bank 22 for exposing the film to a desired dose of UV-C light. Are arranged to pass through.

The oxygen scavenger film may include multiple layers, preferably with an oxidizing organic compound and a transition metal catalyst layer disposed on one side thereof. Multilayer oxygen scavenger films are described in U.S. Patent No. 5,350,622. It is preferable to expose only the oxidizing organic compound and the transition metal catalyst side of the multilayer film to UV-C light. Further, it is preferred that all layers of the multilayer film between the UV-C light source and the oxygen scavenger film are effectively transparent at 254 nm. So,
As shown in FIG. 1, the film path 16 can be arranged so that only one side of the film is exposed to the bank 22 of the bulb 20, but optionally both sides of the film are exposed to the bulb 20. be able to.

Preferably, the film passage 16 is provided between 1 cm and 3 cm, for example a distance of 2 cm from the bank 22 of the bulb 20.

FIG. 2 shows an embodiment of the activation device 10 in which the activation device 10 is included inline in a packaging device. The chamber 9 holds the film 8 from the unwinding roll 12.
And pass the film along the film path 16 to expose it to a source of actinic radiation, for example, a UV-C light source, and the activated film 28 is placed in a packaging device, such as a sealed / gas flash die. / Gas flush
(diess) 24. The activated film 28 is immediately contained as a layer in the package with the forming web 26 supplied from the other components of the package assembly. The sealing / gas flash die 24 is activated to provide a package 30 containing the activated film.
Is applied to the forming web 26.

Optionally, the activation device 10 may be provided with a sensor device 32 for monitoring the dose of UV-C light emitted by the bulb 20. by this,
Deterioration or malfunction of the bulb 20 can be detected. Sensor device 32 may be, for example, an online UV intensity display module (EIT, Inc., Sterling, VA) with a 250-260 nm standard UVI sensor. The sensor device 32 can be linked or operatively associated with a controller for the packaging line, and
The packaging can be automatically interrupted if the -C light output is insufficient.

The bulb 20 preferably has an effective intensity or irradiance E of 0.1 mW / cm ² or less.
The film in the film passage 16 is preferably shielded by
A sleeve member (not shown) is provided to protect the light bulb 20 from contact with a broken element such as the glass of the light bulb 20 if the light bulb 20 is broken. This sleeve may be a shrinkable member or coating applied to the bulb 20. A preferred sleeve is a heat shrunk FEP-Teflon sleeve.

The bulb 20 may be a fluorescent tube-type bulb, preferably having a width sufficient to extend beyond both sides of the width of the film to be processed. The bulb is preferably 36-48
It has a width of inches, which would be suitable for processing films having a width of less than 30 inches to 40 inches. Appropriate bulbs are part names UV-LU
XGRFX5194 sold by Voltarc.

The step of exposing the oxygen scavenger film to actinic radiation can optionally be performed in a stepwise manner, exposing the film for multiple discrete times. This embodiment is useful for packaging machines that operate in intermittent motion, such as the MULTIVAC® R7000 thermoforming machine distributed by KOCH of Kansas City, Missouri. Can be easily adapted.

According to the present invention, organoleptic compounds present in the oxygen scavenger article before or after activation of the oxidizing organic compound in the article and / or occurring as a by-product in the oxygen scavenging activated system (typically Many of the organic volatiles are activated, e.g., during and / or after activation, by treating the article as disclosed herein, thereby activating levels below the threshold, i.e., the taste organs. It has been found that it can be reduced to levels below the concentration of the compound required for GC / MS (Gas Chromatography / Mass Spectrometer) data showed that when the film was exposed to hot water, steam, direct heating and forced hot air, the amount of certain volatile compounds was reduced.

FIGS. 3 and 4 show the results of a test involving a monolayer film activated, then untreated, treated with a heat lamp or treated with heated water.

FIG. 3 shows a chart with three bars appearing. The left bar represents a control film that was activated as described herein and that was not further post-activated. Table 1 identifies the materials used in this monolayer film and the multilayer laminate also described herein.

[0057]

[Table 1]

[0058] Certain materials were blended together for the laminate construction, and these blends had the following formulations. AB ₁ = 80% PE ₁ + 20% (95% PE ₂ + 5% A ₁ ). AB ₂ = 60% PE ₁ + 40% (95% PE ₂ + 5% A ₁ ). PECB ₁ = 50% PEC ₁ + 50% EM ₁ . OSB ₁ = 50% EV ₁ + 40% OS ₁ + 10% (88% EV ₃ + 11.0% C
AT ₁ + 1.0% PI ₁ ). EVB ₁ = 80% EV ₂ + 20% (95% PE ₂ + 5% A ₁ ) This film has 40% OS ₁ , 0.1% cobalt from CAT ₁ and 0%
. It was a monolayer film with a blend of 1% PI ₁ , the remainder being EV ₁ .

The second bar in the center of the graph has the same composition as the control, but immediately after activation,
FIG. 3 represents a film in which the film has been exposed to a heat lamp such that air immediately adjacent to the exposed film surface rises to a temperature of about 77 ° C. for 3 minutes.

The third bar represents a film similar in composition to the first film, but immediately after activation, the film was immersed in water having a temperature of 80 ° C. for 5 minutes. I have.

FIG. 4 shows the analysis results obtained by analyzing the films for special odors and evolving volatiles.

The three bars grouped on the left edge of the chart represent control samples that were not treated. Of the three bars, the leftmost black bar represents vinyl acetate, the middle left sloping bar represents vinylcyclohexene, and the rightmost sloping right bar represents hexanal.

The middle three bars in the chart are of the same composition as the control, but immediately after actuation, the film was exposed to a heat lamp to allow air immediately adjacent to the exposed film surface for 3 minutes. Represents a film that was raised to a temperature of about 77 ° C. Of the three bars, the leftmost bar in this central group represents vinyl acetate, the middle bar represents vinylcyclohexene, and the rightmost bar represents hexanal.

The rightmost bar in this chart represents a film similar in composition to the first film, but immediately after activation, the film was immersed in water at 80 ° C. for 5 minutes. . With the methodology used, no peaks were detected for vinyl acetate and hexanal, and the only bar appearing in this portion of the chart represents the amount of vinylcyclohexene detected.

In each case for the data of FIGS. 3 and 4, the film was analyzed and analyzed by GC / FID.
The data generated by the (flame ionization detector) curve by direct desorption immediately after activation.

FIG. 3 shows a significant reduction in total volatiles, ie, the amount of flavor and non-flavor producing compounds, when the film was exposed to radiant heat or direct heating after UV activation.

Similarly, FIG. 4 shows a significant decrease in the amount of selected flavor generating compounds, ie, vinyl acetate, vinylcyclohexene and hexanal.

The extent to which the reduction of these and other compounds affects the sensory irritation of the film was not evaluated by the analytical methods described herein.

Thus, another experiment was performed to test the effect of post-activation treatment on sensory irritation of the oxygen scavenging film.

A laminate was produced for this purpose.

This laminate was produced by laminating a co-extruded four-layer film to a second film using a common adhesive. The structure of this laminate was as follows.

AB₁/ PECB₁/ OSB₁/ EVB₁// AD₁// F₁  The target (and near actual) standard dimensions (in mils) for each layer of this laminate structure
, And Table 2.

[0073]

[Table 2]

Blower (GAST Standard Reggenair Blower (Standa)
rd Regenair Blower))
(LEISTER LE5000 Electric Hot Air Tool) was adapted to the actuation device described herein. The knife was placed in its closest position, about 3 inches from the film. The temperature of the heated air at the surface of the film was measured at three points about 5 inches, 10 inches and 15 inches from the knife (FIG. 5). The knife angle was set at approximately 45 degrees to the film path. The Multivac R7000 intermittent exercise packaging machine 30 was operated at 4 cycles / min. That is, the film remained stationary at a given point in space for about 13 seconds. The heated air knife was able to maintain a nearly constant surface temperature across the film, regardless of distance. Air temperature was primarily dependent on the air knife thermometer and air flow valve settings.

[0075] Two sets of experiments were performed. For both tests, the film with the oxidizing organic compound was activated at approximately 800 mJ / cm ² in a chamber as described herein. The activated film was then advanced out of the chamber and passed through a hot air knife / blower combination.

For the first experiment, the blower and air knife were adjusted so that the air immediately adjacent to the film surface reached a maximum temperature of 110 ° F. The film is then made into a package containing 200 mL of water, and this is combined with 0.5% O ₂ : 99.
. 5% N ₂ by a gas flush, to simulate field testing conditions.

For the second experiment, the highest temperature that subsequently reached the surface of the film was 200 ° F., and then a package containing 200 mL was made, which was made up to 1% O ₂ : 99%
Were gas flushed with a N _2.

Samples were stored at 40 ° F. and evaluated 18 hours and 7 days after activation. The samples were subjected to sensory evaluation for a three-point test with open comments.

The sensory results showed a significant improvement (P <0.001) in the sensory irritation of the film. For both oxygen residual levels, ie, 0.5% and 1.0%, the improved sensory irritation was not only evident in the package tested 18 hours after actuation, but also tested 1 week later. It was also clear about the package that did. That is, the film was removed for 7 days. In both cases, the panelists indicated by a final open comment that the "heated film" had no or less malodor when compared to the control.

The improvement in organoleptic properties was confirmed by analytical tests. Table 4 includes GCO (Gas Chromatography Olfactory Analysis) and GC / MS data for odor active compounds associated with some oxygen scavenger films. The laminate structure in this study was similar to the multi-layer laminate described earlier herein and had the following structure:

AB₂/ PECB₁/ OSB₁/ EVB₁// AD₁// F₁  The target (and near actual) standard dimensions (in mils) for each layer of this laminate structure
, And Table 3.

[0082]

[Table 3] This data compares volatiles (odorous species) before and after treatment with a hot air knife.

[0083]

[Table 4]

[Table 5]

[Table 6] Initial _{O 2} concentration of all specimens NOTE day 0 for the table 4 were in the range of 1.2 wt% to 1.4 wt%. Approximately 30 compounds were identified in untreated samples (15 hours on day 1 after activation). For the same sample with air knife, only 20 odorants were detected. Nine species were not detected. Seven days after removal of oxygen, 28 odor active compounds were identified in the untreated sample. For the same sample with an air knife, 22 odorants were identified.
Of these 22 odorants, 16 had lower concentrations for the treated (air knife) sample. This is so striking that it explains why the taste panel preferred the water in the treated sample. N / D = not detected. VL = very low area count. Volatiles not detected by the GCO were not included in this data set. These are mostly alkanes and are not involved in odor and taste problems. Area counts are relative. However, they are expected to be proportional to the concentration for a given odor. Even at relative concentrations, the area of one odorant cannot be directly compared to different odorants. The overall effect of the treatment on all odorants is generally more significant than the effect on any one particular odorant. The total area in the bottom row of Table 4 shows a dramatic decrease in total area on both days 1 and 7 when the laminate was treated according to the present invention. For data involving the use of a hot air knife, the temperature of the air at the surface of the film closest to the hot air knife was 180 ° F.

In addition, the removal data (Tables 5 and 6) show that heating the film immediately after activation increases the initial removal rate and allows the film to reach maximum peak speed within 24 hours. According to these experiments, the average speed of the heated film was three times higher on day 1 than the control. The same is true for average oxygen removal capacity. This is important because, although the heated film removed more oxygen on day 1 than the control, it was perceived to have better organoleptic material than the unheated control. After the second day, the average speed of the treated samples and controls was:
The control samples reached their maximum instantaneous speed on the second or third day, so were nearly equal. The final average volume was basically the same for both the treated and untreated films, but the heated film was perceived as being better organoleptically. The measurements for Tables 5 and 6 were made at 40 ° F.

[0085]

[Table 7]

[0086]

[Table 8]

Thus, by using the heat provided by the moving stream of air immediately after activating the oxygen scavenger film, a significant improvement in the sensory irritation of the film was obtained.

As an added advantage, heating the film significantly increased the initial removal rate.

The data in Tables 5 and 6 are also significant in that it is important to remove oxygen from the interior atmosphere of the package as soon as possible after packaging. Increased speed and volume on the first day is provided, leading to a decrease in the oxygen content inside the package more quickly than in the control, thus further enhancing the utility of the present invention. .

In another embodiment (see FIG. 6), the oxygen scavenging film passes from an activation chamber, generally designated 9, which advances out of chamber 9 along film path 40. , Through the water or chemical bath 42 containing the material 44. The treatment medium 44 picks up, absorbs, adsorbs, sequesters, blocks, dissolves, and carries away the amount of organic low molecular weight extractables on or in the film when in contact with the surface of the activated film. Or any other suitable solid or liquid that is otherwise reduced. Examples of materials 44 include liquids such as water and hydrogen peroxide solutions and hydrous silicates (eg, vermiculite), amorphous silica, zeolites,
Solids such as hydrotalcite and activated carbon are included. Preferably, material 44
Is heated water, more preferably 71 ° F to 212 ° F, for example, 100 ° F to 200 ° F.
水 F, most preferably water having a temperature between 140 ゜ F and 180 ゜ F. The removal or removal of low molecular weight extractables can be further improved by circulating or stirring the processing medium or by certain substitutions to maintain extractable concentrations at low levels.

When using bath 42, it is preferable to draw the film through the bath and then run the film through squeeze rollers 46 to remove excess liquid or solids from the film surface. The film can be further dried, if necessary, by passing the film through heated rollers 48, 49 and / or by passing the film past an air blower 50. An alternative is to use a doctor blade or other mechanical device to remove any excess material 44. Yet another alternative is to use a vacuum chamber.

When using a hot air knife 34, this air is preferably between 140 ° F. and 18 ° F.
0 ° F. temperature. Other heated gases, such as nitrogen, can also be used.

In the packaging line 30, the activated and processed film is used to package the oxygen-sensitive product, and then the finished package is advanced to a conveyor or other suitable means for further processing. Let it.

[0094] Packaging systems are generally known in the art and need not be described further herein. The present invention can be used in conjunction with any suitable packaging system.

Also, after processing the article, it can be stored (in the case of film, by rewinding the film) in a suitable environment for later use. However, the oxygen scavenging capacity of the article will typically decrease over time as the oxygen scavenger is activated and begins to scavenge oxygen.

[0096] Means for heating (not shown) can optionally be used to raise the temperature of chamber 9 to at least 55 ° F while film 8 is activated in the chamber. . Means for heating include, for example, a consumer or commercial heating blower or heat gun, an infrared heater, a temperature controlled cartridge heater with a suitable air circulation system, a closed hot water circulation system that exchanges heat with the atmosphere inside the chamber. Or any suitable means, including any other suitable heating means.

The means for treating, whether a solid, liquid or gas, is preferably heated, but has a fluid contact flush (gas or liquid or fragile) to carry away extractables from the surface. Due to the shape of the solid) some improvement in sensory irritation can be obtained even at lower temperatures, for example at room temperature. If a liquid is used as the processing medium, it is believed that the benefits can be attributed to the solvation of the extractables in the processing medium.

In some cases, the treatment can be advantageously performed at temperatures below room temperature, such as 50 ° F., 40 ° F., and 32 ° F., depending on the nature of the processing medium.

The present invention is not limited to the examples described herein, and these examples are to be considered merely as examples, permitting modifications in shape, size, arrangement of parts and operational details.

For example, while the invention has been described in its preferred embodiment, such as a film treated on its major surface, the film can be treated along any and all surfaces. For example, a film can be treated on both sides of its major surface. This can be performed by any suitable means, such as repeating the processing steps after the first pass, while rotating the film to expose the untreated surface. Also, both major surfaces of the film can be treated simultaneously using a pair of hot air knives. Any combination of the means for processing disclosed herein can be used. When the film is in the form of a tube, the outside of the tube, the inside or both sides of the tube can be treated. Of course,
When immersing the article in a liquid bath, the entire outer surface of the activated article will be treated.

The means for advancing an article, such as a film, towards the means for processing from the chamber, and optionally to the means for removing excess processing medium, may be an endless belt, a drive or an idler. It may be of any suitable type, including rollers, nip rollers, and the like. Because the present invention is typically used in conjunction with a packaging machine, in some cases the packaging machine itself provides means for advancing the article toward the processing means and / or the article from the surface of the treated article. It can be considered as a means for advancing towards the means for removing the processing medium.

Although the invention has been described as useful in conjunction with an intermittent motion packaging machine, it can also be used advantageously with a continuous motion machine. Thus, the residence time for the film, i.e., the time that the film is exposed to the processing medium, varies greatly depending on the packaging system, and may be from 1 second or less to 3-4 seconds, 20 seconds or more. The processing speed, temperature and other parameters can be adjusted appropriately taking into account this change.

Those skilled in the art, after examining the present invention, will, through routine experimentation, determine the specific processing medium to be used; the chemical composition, structural arrangement and shape of the article (film, gasket, etc.) to be treated; Exposure conditions; temperature at which the processing step is performed; velocity of the article as it passes by or through the means for processing; velocity of the processing medium;
Optimal processing conditions will depend on several factors, including the target level of extractables in the final article; the type of product being packaged, and the like. By way of example, gaskets of the type disclosed herein may have higher temperature resistance than typical packaging films,
It can be processed in an optionally heated liquid medium.

Those skilled in the art will recognize that articles, such as films, have a limited ability to undergo heat, fluid, or other treatment without significant degradation of the physical properties or performance of the film. When the solid material is the processing medium, the activated article can be advanced through a mass of material, which is preferably maintained at a temperature between 32 ° F. and 300 ° F. . Also, the film or other article can be advanced between rollers containing or carrying the treatment material. Temperatures below and above this temperature range may in some cases be effective in reducing organoleptic compounds in the activation process, but at higher temperatures damage to the film or degradation of film properties The danger increases. The same is true for higher temperature fluids (gases and liquids).

It will be appreciated that processing at higher temperatures requires shorter processing times to perform comparable improvements in organic extractables levels.

The articles to be treated must not physically degrade to any substantial extent as a result of the processing step and must not have their performance characteristics degraded. An example is a process that renders a treated article unsuitable for its intended commercial use. Therefore,
As a general rule, chemical or physical reagents that cause such degradation are not suitable for use in connection with the present invention. However, the nature and degree of degradation and the intended end use will determine the suitability of the process. For example, the substantial degradation of optical properties (haze, gloss, clarity) in a transparent flexible film is nevertheless the treated material laminated to a metal foil and the optical properties If the loss becomes of less commercial significance, it is acceptable.

[0107] Any combination of treatments can be used. An example is a liquid bath followed by heated air. In this case, heated air can be used to dry excess liquid from the article surface and further treat the article.

[Brief description of the drawings]

FIG. 1 schematically illustrates an apparatus useful in connection with the present invention.

FIG. 2 schematically illustrates an apparatus useful in connection with the present invention.

FIG. 3 graphically illustrates the reduction of odor generating volatiles according to the present invention.

FIG. 4 graphically illustrates the reduction of odor generating volatiles according to the present invention.

FIG. 5 schematically illustrates a method and apparatus according to the present invention.

FIG. 6 schematically illustrates a method and apparatus according to the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HU, ID, IL, IS, JP, KE, KG, KP, KR , KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW Drive 8 (72) Inventor Sylvia, Earl Carina United States, South Carolina 29607, Greenville, Gateway Boulevard Number 117.100 (72) Inventor Thomas, Jeffrey A. United States, South Carolina・ 29650, Glia, West Poinsett Street ・ 1102, apartment number ・ 87 F term (reference) 4F073 AA32 BA07 BA0 8 BA11 BA13 BA18 BA19 BA24 BB01 CA45 DA01 DA09 EA11 EA52 4F201 AB16 AB17 AB18 AC03 AG01 AH54 AK04 AP19 AR06 BA07 BC01 BC02 BC06 BC07 BC13 BC37 BQ22 BQ42 BQ53 BR31 BR34 BR36 BR50

Claims (20)

[Claims] 1. A) providing an article containing an oxidizing organic compound and a organoleptic compound; b) advancing the article toward a means for treating the article;
The means for treating the article includes a treatment medium and a means for applying the treatment medium to the article; and c) applying the treatment medium to the surface of the article to reduce the amount of organoleptic compounds in the article. A method comprising: 2. The method of claim 1, wherein the article comprises a film. 3. The method of claim 1, comprising applying a treatment medium to the surface of the article after exposing the article to a source of actinic radiation. 4. The method of claim 3, comprising exposing the article to a source of actinic radiation while the article is in the chamber. 5. The method according to claim 4, comprising advancing the article out of the chamber in the direction of the means for treating the article. 6. The method of claim 1, comprising applying a treatment medium to the surface of the article by contacting the surface of the article with a gas having a temperature between 32 ° F. and 300 ° F. at the surface of the article. The described method. 7. The method of claim 1, comprising applying a treatment medium to the surface of the article by contacting the film surface of the article with a liquid having a temperature between 32 ° F. and 212 ° F. 8. The method of claim 1, comprising applying a treatment medium to the surface of the article by contacting a film surface of the article with a solid having a temperature between 32 ° F. and 300 ° F. 9. The method of claim 1, comprising applying the treatment medium to a surface of the article by moving the article between rollers having a surface temperature between 32 ° F. and 300 ° F. 10. After applying the treatment medium to the surface of the article, the article is further advanced to means for removing the treatment medium from the surface of the article, and removing some of the treatment medium from the surface of the article. The method of claim 1, comprising: 11. A means for treating an article containing an oxidizing organic compound and a organoleptic compound so as to reduce the amount of organoleptic compound in the article, wherein the article is for treating the article. Means include: i) a processing medium; and ii) means for applying the processing medium to a surface of the article; and b) means for advancing the article toward means for processing the article. apparatus. 12. A method for emitting actinic radiation comprising: a) means for emitting actinic radiation; and b) means for advancing the article toward means for emitting actinic radiation to obtain an activated article. An apparatus according to claim 11. 13. The apparatus according to claim 12, comprising a chamber in which means for emitting actinic radiation are located. 14. The apparatus according to claim 12, comprising means for emitting ultraviolet light. 15. A treatment medium comprising: i) a gas having a temperature between 32 ° F. and 300 ° F. at the surface of the article; ii) a liquid having a temperature between 32 ° F. and 212 ° F. at the surface of the article; iii. 12. The apparatus of claim 11, comprising: a surface of the article comprising a solid having a temperature between 32 ° F and 300 ° F and iv) sensible heat. 16. The apparatus of claim 15, wherein the processing medium comprises a gas selected from the group consisting of air, nitrogen, and steam. 17. The apparatus according to claim 15, wherein the processing medium comprises a liquid selected from the group consisting of water and a hydrogen peroxide solution. 18. A treatment medium comprising a hydrated silicate, an amorphous silica, a zeolite,
2. The composition of claim 1, comprising a solid selected from the group consisting of hydrotalcite and activated carbon.
An apparatus according to claim 5. 19. The apparatus of claim 11, wherein the means for processing the article includes a pair of rollers for advancing the article therebetween, the roller having a temperature between 32 ° F. and 300 ° F. 20. A means for applying the treatment medium to the surface of the article, comprising: a) a container in which the treatment medium is located; b) a blower capable of directing a fluid toward the surface of the article; c) The apparatus of claim 11, wherein the apparatus is selected from the group consisting of a pair of rollers and d) a ramp.